JPS63233945A - Selective hydroformylation of diolefin - Google Patents
Selective hydroformylation of diolefinInfo
- Publication number
- JPS63233945A JPS63233945A JP62068551A JP6855187A JPS63233945A JP S63233945 A JPS63233945 A JP S63233945A JP 62068551 A JP62068551 A JP 62068551A JP 6855187 A JP6855187 A JP 6855187A JP S63233945 A JPS63233945 A JP S63233945A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- vinylbenzene
- phenyl
- propionaldehyde
- complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000007037 hydroformylation reaction Methods 0.000 title claims description 11
- 150000001993 dienes Chemical class 0.000 title description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 16
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- SWMVJOXVIGSMEN-UHFFFAOYSA-N 3-phenylbuta-1,3-dienylbenzene Chemical compound C=1C=CC=CC=1C(=C)C=CC1=CC=CC=C1 SWMVJOXVIGSMEN-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 8
- 238000005810 carbonylation reaction Methods 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 230000006315 carbonylation Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 abstract description 21
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 7
- 229910052703 rhodium Inorganic materials 0.000 abstract description 5
- 229910052741 iridium Inorganic materials 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract 2
- 230000007704 transition Effects 0.000 abstract 2
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 229910052750 molybdenum Inorganic materials 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 229910052702 rhenium Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 29
- -1 phenoxyphenyl Chemical group 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 5
- 125000003963 dichloro group Chemical group Cl* 0.000 description 5
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000002923 oximes Chemical class 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- DXIJMSTWIULOJH-UHFFFAOYSA-N 1-ethenyl-3-(1-phenylethenyl)benzene Chemical group C=CC1=CC=CC(C(=C)C=2C=CC=CC=2)=C1 DXIJMSTWIULOJH-UHFFFAOYSA-N 0.000 description 1
- LHNRWGOBPNCPKQ-UHFFFAOYSA-N 4-phenylbut-1-en-3-ynylbenzene Chemical compound C=1C=CC=CC=1C#CC=CC1=CC=CC=C1 LHNRWGOBPNCPKQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- QRDGENWBAUNKHS-UHFFFAOYSA-N C=1C=CC=CC=1C=CC=CC1(OCC)CC=CC=C1 Chemical compound C=1C=CC=CC=1C=CC=CC1(OCC)CC=CC=C1 QRDGENWBAUNKHS-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000004989 dicarbonyl group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ISCGKQXZXYUYAW-UHFFFAOYSA-M magnesium;ethenylbenzene;bromide Chemical compound [Mg+2].[Br-].C=CC1=CC=C[C-]=C1 ISCGKQXZXYUYAW-UHFFFAOYSA-M 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、選択的ヒドロフオルミル化方法に関する。更
に詳しくは、ジオレフィンをカルボニル化して選択的に
不飽和アルデヒドを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a selective hydroformylation process. More specifically, the present invention relates to a method for selectively producing unsaturated aldehydes by carbonylating diolefins.
（従来技術とその問題点）
従来から、オレフィンを一酸化炭素及び水素と反応させ
アルデヒドを製造するヒドロフオルミル化方法は、例え
ば、モノオレフィン等に対して広く工業的に行われてい
る。(Prior Art and its Problems) Conventionally, hydroformylation methods for producing aldehydes by reacting olefins with carbon monoxide and hydrogen have been widely used industrially, for example, for monoolefins.
秋るに、ジオレフィンに対しては、その例が少ない。例
えば、特開昭５８−２１００３３号公報及び同５９−１
１０６４３号公報では、５−エチリデンビシクロ［２，
２，１］へブテン−２を反応させてはいるが、それが有
する２つの不飽和基にフォルミル基が導入されることが
開示されている。In the fall, there are few examples of this for diolefins. For example, JP-A-58-210033 and JP-A-59-1
10643, 5-ethylidenebicyclo[2,
2,1]hebutene-2 is reacted, but it is disclosed that a formyl group is introduced into two unsaturated groups that it has.
同公報では、水素や一酸化炭素の導入量を調整すること
により、その１つの不飽和基にフォルミル基を導入して
いる。In this publication, a formyl group is introduced into one of the unsaturated groups by adjusting the amount of hydrogen and carbon monoxide introduced.
本発明者らは、特定の構造のジオレフィンならば、一酸
化炭素と水素とを反応させても、その一方の不飽和基の
みにしかフォルミル基が導入されないことを見出し本発
明を完成させたものである。The present inventors have completed the present invention by discovering that if a diolefin has a specific structure, even if carbon monoxide and hydrogen are reacted, a formyl group is introduced only into one of the unsaturated groups. It is something.
（発明の構成）
即ち、本発明は、下記式（Ｉ）で表される（１−アリー
ルエテニル）ビニルベンゼンを、遷移金属錯体カルボニ
ル化触媒の存在下に、水素及び一酸化炭素と反応させる
ことにより下記式（ｎ）で表されるα−（（１−アリー
ルエテニル）フェニル）プロピオンアルデヒドを製造す
ることを特徴とする選択的ヒドロフオルミル化方法に間
するものである。(Structure of the Invention) That is, the present invention involves reacting (1-arylethenyl)vinylbenzene represented by the following formula (I) with hydrogen and carbon monoxide in the presence of a transition metal complex carbonylation catalyst. This is a selective hydroformylation method characterized by producing α-((1-arylethenyl)phenyl)propionaldehyde represented by the following formula (n).
Ｈ２ Ｈ２ （式中Ｒはアリール基） 以下に本発明を更に説明する。H2 H2 (In the formula, R is an aryl group) The invention will be further explained below.
上記の（１−アリールエテニル）ビニルベンゼンにおけ
るアリール基Ｒには、フェニル、アルキルフェニル、ア
ルコキシフェニル、フェノキシフェニル、ビフェニル等
のアリール基の他に、フェニル基に種々の置換基の置換
したアリール基が挙げられる。このような置換基として
は、カルボキシル基、水酸基、アルコキシ基及びアルコ
キシカルボニル基等が例示される。The aryl group R in the above (1-arylethenyl)vinylbenzene includes aryl groups such as phenyl, alkylphenyl, alkoxyphenyl, phenoxyphenyl, and biphenyl, as well as aryl groups substituted with various substituents on the phenyl group. can be mentioned. Examples of such substituents include carboxyl groups, hydroxyl groups, alkoxy groups, and alkoxycarbonyl groups.
具体的には、上記（１−アリールエテニル）ビニルベン
ゼンには、フェニル、トリル、キシリル等をアリール基
として有する（１−フェニルエチニル）ビニルベンゼン
、（１−トリルエチニル）ビニルベンゼン、（１−キシ
リルエチニル）ビニルベンゼン、（１−エチルフェニル
エチニル）ビニルベンゼン等の他に、（１−ヒドロキシ
フェニルエチニル）ビニルベンゼン、（１−メトキシフ
ェニルエチニル）ビニルベンゼン、（１−ジメトキシフ
ェニルエチニル）ビニルベンゼン、（１−エトキシフエ
ニルエテニル）ビニルベンゼン、（１−カルボキシフェ
ニルエチニル）ビニルベンゼン、（１−メトキシカルボ
ニルフェニルエチニル）ビニルベンゼン、（１−ジ（メ
トキシカルボニル）フェニルエチニル）ビニルベンゼン
、及び（１−エトキシ力ルポニルフェニルエテニル）ビ
ニルベンゼン等が挙げられる。Specifically, the above (1-arylethenyl)vinylbenzene includes (1-phenylethynyl)vinylbenzene, (1-tolylethynyl)vinylbenzene, (1- In addition to (xylylethynyl)vinylbenzene, (1-ethylphenylethynyl)vinylbenzene, etc., (1-hydroxyphenylethynyl)vinylbenzene, (1-methoxyphenylethynyl)vinylbenzene, (1-dimethoxyphenylethynyl)vinylbenzene , (1-ethoxyphenylethenyl)vinylbenzene, (1-carboxyphenylethynyl)vinylbenzene, (1-methoxycarbonylphenylethynyl)vinylbenzene, (1-di(methoxycarbonyl)phenylethynyl)vinylbenzene, and ( Examples thereof include 1-ethoxy(polonylphenylethenyl)vinylbenzene and the like.
なお、上記化合物には、その置換基の置換位置による位
置異性体も含まれるものであるが、好ましくはｍ−異性
体である。Although the above compound includes positional isomers depending on the position of the substituent, m-isomer is preferable.
本発明の方法により、選択的にビニル基がヒドロフオル
ミル化されることにより、前記式の化合物（■）が製造
される。又、前記式（Ｉ）において、アリール基がアル
キル基等では何れの二重結合もヒドロフオルミル化され
る。According to the method of the present invention, the vinyl group is selectively hydroformylated to produce the compound (■) of the above formula. Further, in the above formula (I), when the aryl group is an alkyl group, any double bond is hydroformylated.
本発明のヒドロフオルミル化反応により、訂記式（Ｉ）
の化合物は、それが有するビニル基のみが選択的にヒド
ロ７オルミル化され、アリール基の置換したエチニル基
は、該反応においては実質的に何等の反応もしない。By the hydroformylation reaction of the present invention, the formula (I)
In the compound, only the vinyl group thereof is selectively hydro7-ormylated, and the ethynyl group substituted with the aryl group does not substantially undergo any reaction in this reaction.
従って、本発明の反応により製造される化合物は、前記
式（Ｉ）で示された化合物のビニル基にフォルミル基と
水素原子が付加した化合物となる。Therefore, the compound produced by the reaction of the present invention is a compound in which a formyl group and a hydrogen atom are added to the vinyl group of the compound represented by formula (I).
特にフォルミル基の付加位置は、通常ビニル基のα−位
である。In particular, the attachment position of the formyl group is usually the α-position of the vinyl group.
従って、本発明の方法により製造される化合物α−（（
１−アリールエテニル）フェニル）プロピオンアルデヒ
ドは、具体的には、前記の化合物に対応した化合物であ
って、例えばα−（３−（１−フェニルエチニル）フェ
ニル）プロピオンアルデヒド、α−（３−（１−トリル
エチニル）フェニル）プロピオンアルデヒド、α−（３
−（１−キシリルエチニル）フェニル）プロピオンアル
デヒド、α−（３−（１−エチルフェニルエチニル）フ
ェニル）プロピオンアルデヒド、α−（３−（１−ヒド
ロキシフェニルエチニル）フェニル）プロピオンアルデ
ヒド、α−（３−（１−メトキシフェニルエチニル）フ
ェニル）プロピオンアルデヒド、α−（３−（１−ジメ
トキシフェニルエチニル）フェニル）プロピオンアルデ
ヒド、α−（３−（１−エトキシフェニルエチニル）フ
ェニル）プロピオンアルデヒド、α−（３−（１−カル
ボキシフェニルエチニル）フェニル）プロピオンアルデ
ヒド、α−（３−（１−メトキシカルボニルフェニルエ
チニル）フェニル）プロピオンアルデヒド、α−（３−
（１−ジ（メトキシカルボニルフェニルエチニル）フェ
ニル）プロピオンアルデヒド及びα−（３−（１−エト
キシ力ルポニルフェニルエテニル）フェニル）プロピオ
ンアルデヒド等である。Therefore, the compound α-(((
Specifically, 1-arylethenyl)phenyl)propionaldehyde is a compound corresponding to the above-mentioned compounds, such as α-(3-(1-phenylethynyl)phenyl)propionaldehyde, α-(3- (1-Tolylethynyl)phenyl)propionaldehyde, α-(3
-(1-xylylethynyl)phenyl)propionaldehyde, α-(3-(1-ethylphenylethynyl)phenyl)propionaldehyde, α-(3-(1-hydroxyphenylethynyl)phenyl)propionaldehyde, α-( 3-(1-methoxyphenylethynyl)phenyl)propionaldehyde, α-(3-(1-dimethoxyphenylethynyl)phenyl)propionaldehyde, α-(3-(1-ethoxyphenylethynyl)phenyl)propionaldehyde, α- (3-(1-Carboxyphenylethynyl)phenyl)propionaldehyde, α-(3-(1-methoxycarbonylphenylethynyl)phenyl)propionaldehyde, α-(3-
(1-di(methoxycarbonylphenylethenyl)phenyl)propionaldehyde and α-(3-(1-ethoxycarbonylphenylethenyl)phenyl)propionaldehyde.
次にヒドロフオルミル化の条件を説明する。Next, the conditions for hydroformylation will be explained.
使用される錯体触媒としては、Ｎ１、Ｇｏ、 Ｆｅ、Ｍ
ｏ、ＰＬ、Ｒｈ、 Ｉｒ、 ＲＩＪ、Ｒｅ等の遷移金属
の錯体、好ましくは、ＰＬ、Ｒｈ、Ｉｒ、 Ｒｕ等の貴
金属の錯体である。The complex catalysts used include N1, Go, Fe, M
A complex of a transition metal such as O, PL, Rh, Ir, RIJ, Re, etc., preferably a complex of a noble metal such as PL, Rh, Ir, Ru, etc.
遷移金属としては、酸価数はＯから最高位酸価数まで使
用でき、ハロゲン原子、３僅のリン化合物、π−アリル
基、アミン、ニトリル、オキシム、オレフィン、水素あ
るいは一酸化炭素を配位子として含有するものが用いら
れる。As transition metals, the acid number can range from O to the highest acid number, and halogen atoms, phosphorus compounds, π-allyl groups, amines, nitriles, oximes, olefins, hydrogen, or carbon monoxide can be coordinated. Those contained as children are used.
遷移金属錯体触媒の具体例としては、ビストリフェニル
ホスフィンジクロロ錯体、ビストリブチルホスフィンジ
クロロ錯体、ビストリシクロへキシルホスフィンジクロ
ロ錯体、π−アリルトリフェニルホスフィンジクロロ錯
体、トリフェニルホスフィンピペリジンジクロロ錯体、
ビスベンゾニトリルジクロロ錯体、ビスシクロへキシル
オキシムジクロロ錯体、１，５．９−シクロドデカトリ
エン−ジクロロ錯体、ビストリフェニルホスフィンジカ
ルボニル錯体、ビストリフェニルホスフィンアセテート
錯体、ビストリフェニルホスフィンシナイトレート錯体
、ビストリフェニルホスフィンスルフアート錯体、テト
ラキストリフェニルホスフィン錯体、及び一酸化炭素を
配位子の一部に持つクロロカルボニルビストリフェニル
ホスフィン錯体、ヒドリドカルボニルトリストリフェニ
ルホスフィン錯体、ビスタロロチトラカルボニル錯体、
ジカルボニルアセチルアセトナート錯体等を挙げること
ができる。Specific examples of transition metal complex catalysts include bistriphenylphosphine dichloro complex, bistributylphosphine dichloro complex, bistricyclohexylphosphine dichloro complex, π-allyltriphenylphosphine dichloro complex, triphenylphosphine piperidine dichloro complex,
Bisbenzonitrile dichloro complex, biscyclohexyloxime dichloro complex, 1,5.9-cyclododecatriene-dichloro complex, bistriphenylphosphine dicarbonyl complex, bistriphenylphosphine acetate complex, bistriphenylphosphine cinitrate complex, bistriphenylphosphine Sulfate complexes, tetrakistriphenylphosphine complexes, chlorocarbonylbistriphenylphosphine complexes having carbon monoxide as part of the ligand, hydridocarbonyltristriphenylphosphine complexes, bistalolotitracarbonyl complexes,
Dicarbonylacetylacetonate complexes and the like can be mentioned.
また、反応系において上記の錯体を形成し得る化合物も
反応系に供給することにより用いることができる。すな
わち、上記遷移金属の酸化物、硫酸塩、塩化物等に対し
て配位子となり得る化合物、すなわち、ホスフィン、ニ
トリル、アリル化合物、アミン、オキシム、オレフィン
、あるいは一酸化炭素を同時に反応系に存在させる方法
である。Further, a compound capable of forming the above-mentioned complex in the reaction system can also be used by supplying it to the reaction system. That is, compounds that can serve as ligands for the oxides, sulfates, chlorides, etc. of the transition metals, such as phosphines, nitriles, allyl compounds, amines, oximes, olefins, or carbon monoxide, are simultaneously present in the reaction system. This is the way to do it.
上記の配位子となり得る化合物としてのホスフィンとし
ては、例えば、トリフェニルホスフィン、トリトリルホ
スフィン、トリブチルホスフィン、トリシクロヘキシル
ホスフィン、トリエチルホスフィン等、ニトリルとして
は、例えば、ベンゾニトリル、アクリロニトリル、プロ
ピオニトリル、ベンジルニトリル等、アリル化合物とし
ては、例えば、アリルクロライド、アリルアルコール等
、アミンとしては、例えば、ベンジルアミン、ピリジン
、ピペラジン、トリーローブチルアミン等、オキシムと
しては、シクロへキシルオキシム、アセトオキシム、ベ
ンズアルドオキシム等、オレフィンとしては１．５−シ
クロオクタジエン、Ｌ、５．９−シクロデカトリエン等
が挙げられる。Examples of the phosphine as a compound that can serve as the above-mentioned ligand include triphenylphosphine, tritolylphosphine, tributylphosphine, tricyclohexylphosphine, triethylphosphine, etc.; examples of the nitrile include benzonitrile, acrylonitrile, propionitrile, Examples of allyl compounds such as benzyl nitrile include allyl chloride and allyl alcohol; examples of amines include benzylamine, pyridine, piperazine, and trilobylamine; examples of oximes include cyclohexyloxime, acetoxime, and benzaldo. Examples of olefins such as oximes include 1,5-cyclooctadiene, L, 5,9-cyclodecatriene, and the like.
錯体触媒、または錯体を作り得る化合物の使用量は、（
１−アリールエテニル）ビニルベンゼン（式Ｉ）１モル
に対して０．０００１〜０．５モル、好ましくは０．０
０１〜０．１モルである。また、錯体を作り得る化合物
を使用する場合の配位子となり得る化合物の添加量は、
錯体を作り得る化合物１モルに対して０．８〜１０モル
、好ましくは１〜４モルである。The amount of complex catalyst or compound that can form a complex is (
1-arylethenyl)vinylbenzene (Formula I) 0.0001 to 0.5 mol, preferably 0.0 mol per mol of vinylbenzene (formula I)
01 to 0.1 mole. In addition, when using a compound that can form a complex, the amount of the compound that can be a ligand is:
The amount is 0.8 to 10 mol, preferably 1 to 4 mol, per mol of the compound capable of forming a complex.
更に、反応速度を向上させるで目的で、塩化水素、三弗
化ホウ素等の無機ハロゲン化物やヨウ化メチル等の存機
ヨウ化物等を添加することができる。Furthermore, in order to improve the reaction rate, inorganic halides such as hydrogen chloride and boron trifluoride, and residual iodides such as methyl iodide can be added.
これらハロゲン化物を添加する場合は、錯体触媒、また
は錯体を作り得る化合物１モルに対して、ハロゲン原子
として０，１〜３０倍モル、好ましくは１〜１５倍モル
使用する。添加量が０．１モル未満の場合、触媒の種類
によっても異なるが、添加の効果が見られないことがあ
る。また、３０倍モルを越えるときは、触媒活性が却っ
て低下すると共に、（１−アリールエテニル）ビニルベ
ンゼン（式１）の二重結合にハロゲンが付加する等目的
の反応が抑制される。When these halides are added, they are used in an amount of 0.1 to 30 times the halogen atom, preferably 1 to 15 times the mole, per mole of the complex catalyst or the compound capable of forming a complex. If the amount added is less than 0.1 mol, the effect of the addition may not be seen, although it varies depending on the type of catalyst. On the other hand, when the amount exceeds 30 times the mole, the catalytic activity is rather reduced and the desired reaction is suppressed, such as by addition of halogen to the double bond of (1-arylethenyl)vinylbenzene (Formula 1).
カルボニル化反応は、反応温度は４０〜１５０℃、好ま
しくは５５〜１１０℃で行う。反応温度が４０℃未満で
は、反応速度が著しく遅くなり、実用上実施することが
できない。また１５０℃を越える温度では、重合、水素
付加等の副反応や錯体触媒の分解が生じ好ましくない。The carbonylation reaction is carried out at a reaction temperature of 40 to 150°C, preferably 55 to 110°C. If the reaction temperature is less than 40° C., the reaction rate will be extremely slow and the reaction cannot be carried out practically. Furthermore, temperatures exceeding 150°C are undesirable because side reactions such as polymerization and hydrogenation and decomposition of the complex catalyst occur.
反応圧力は５ ｋｇ／ａｍ２以上であれば、適宜選択で
きる。５ ｋｇ／ｃａ＋２未満では、実用上実施するこ
とができない程反応が遅くなる。また圧力は高い程反応
が速やかに進行し好ましいが、高過ぎる圧力は反応器の
耐圧を非常に高くする必要がでてくるなど、製造装置の
点から自ずと限界がある。従って実用上は５００ ｋｇ
／ｃｍ２以下の圧力で充分である。The reaction pressure can be appropriately selected as long as it is 5 kg/am2 or more. If it is less than 5 kg/ca+2, the reaction becomes so slow that it cannot be practically implemented. Further, the higher the pressure, the more quickly the reaction proceeds, which is preferable, but too high a pressure naturally has its limits in terms of production equipment, such as the need to make the pressure resistance of the reactor extremely high. Therefore, in practice it is 500 kg.
A pressure of less than /cm2 is sufficient.
反応は一酸化炭素および水素の混合ガスの吸収による圧
力減少がみられなくなるまで行えばよく、通常は４〜２
０時間の反応時間で充分ある。The reaction may be carried out until no pressure decrease is observed due to the absorption of the mixed gas of carbon monoxide and hydrogen, which is usually 4 to 2 hours.
A reaction time of 0 hours is sufficient.
反応に必要な一酸化炭素と水素とは、あらかじめ混合さ
れた混合ガスの状態でも、各別に反応器に供給してもよ
い。反応系に供給する場合の一酸化炭素と水素のモル比
は、適宜選択できる。すなわちヒドロフオルミル化反応
では、一酸化炭素と水素とは正確に１：１のモル比で吸
収消費されて行く。従って、過剰に供給された成分が反
応せずに残留するため、圧力減少が認められなくなった
時点で他方の成分を供給すれば再び反応が進行する。従
って、反応器の大きさ、反応の形式にもよるが、一酸化
炭素対水素のモル比は！＝１で供給すれば最も効率的で
ある。Carbon monoxide and hydrogen required for the reaction may be supplied to the reactor separately, either in the form of a mixed gas that has been mixed in advance. The molar ratio of carbon monoxide and hydrogen when supplied to the reaction system can be selected as appropriate. That is, in the hydroformylation reaction, carbon monoxide and hydrogen are absorbed and consumed in a precisely 1:1 molar ratio. Therefore, since the component supplied in excess remains unreacted, if the other component is supplied once the pressure decrease is no longer observed, the reaction will proceed again. Therefore, depending on the size of the reactor and the type of reaction, the molar ratio of carbon monoxide to hydrogen is! It is most efficient if it is supplied with =1.
本発明のヒドロフオルミル化方法において、カルボニル
化に不活性な溶媒を反応熱除去等の目的で用いることも
できる。カルボニル化に不活性な溶媒としては、エーテ
ル、ケトン、アルコール等の極性溶媒や、パラフィン、
シクロパラフィン、芳香族炭化水素のような無極性溶媒
が挙げられる。In the hydroformylation method of the present invention, a solvent inert to carbonylation can also be used for purposes such as removing reaction heat. Examples of inert solvents for carbonylation include polar solvents such as ethers, ketones, and alcohols, paraffins,
Examples include nonpolar solvents such as cycloparaffins and aromatic hydrocarbons.
しかし、一般には無溶媒の状態で充分好ましい結果が得
られる。However, in general, sufficiently favorable results can be obtained without a solvent.
ヒドロフオルミル化反応の終了後、反応物は、好ましく
は減圧下で蒸留分離すれば、容易に目的生成物であるα
−（３−ベンゾイルフェニル）プロピオンアルデヒド（
式■）と触媒とに分離することができる。回収された錯
体触媒は再度カルボニル化反応に使用することもできる
。After the completion of the hydroformylation reaction, the reaction product can be easily separated by distillation, preferably under reduced pressure, to obtain the desired product α.
-(3-benzoylphenyl)propionaldehyde (
Formula ■) and the catalyst can be separated. The recovered complex catalyst can also be used again in the carbonylation reaction.
（発明の効果）
本発明によれば、ビニル基をも有するジオレフィンであ
る化合物の前記式（Ｉ）で示される（１−アリールエテ
ニル）ビニルベンゼンは選択的にヒドロフオルミル化さ
れる。即ちそのビニル基のみがヒドロフオルミル化され
眞記式（ｎ）で表されるα−（（１−アリールエテニル
）フェニル）プロビオンアルヂ）−犀が郭；青水れ乙−
以下に、実施例により本発明を説明する。(Effects of the Invention) According to the present invention, (1-arylethenyl)vinylbenzene represented by the above formula (I), which is a diolefin compound that also has a vinyl group, is selectively hydroformylated. That is, only the vinyl group is hydroformylated to form α-((1-arylethenyl)phenyl)probionaldi)-((1-arylethenyl)phenyl)-probionaldi)-
The present invention will be explained below with reference to Examples.
参考製造例１
ｌ−（３−ビニルフェニル）−１−
フェニルエチレンの合成
滴下漏斗、還流冷却器、及び攪拌機付きの２１三つロフ
ラスコ中に、金属マグネシウム２５．５ｇ（１，０５モ
ル）を入れ、乾燥窒素を流して、充分乾燥した後、モレ
キュラーシーヴ５Ａで乾燥したテトラヒドロフラン５０
ｎ＋１を入れて激しく攪拌す・る。しかる後に臭化３−
ビニルベンゼ：／ １８３ ｇ（１，０モル）の乾燥テ
トラヒドロフラン５００ｍ１溶液を２時間かけて徐々に
滴下した。反応温度は７５℃〜８０℃に保ち、該溶液滴
下終了後も、そのままで更に−・時間攪拌を続けた。こ
のようにして得たグリニヤール試薬、臭化３−ビニルフ
ェニルマグネシウム溶液中に、更にアセトフェノン１２
２．６ｇ （１，０２モル）の乾燥テトラヒドロフラン
５００ｍ１溶液を２時間かけて徐々に滴下した。Reference Production Example 1 Synthesis of l-(3-vinylphenyl)-1-phenylethylene 25.5 g (1.05 mol) of metallic magnesium was placed in a 21-hole flask equipped with a dropping funnel, a reflux condenser, and a stirrer. , thoroughly dried by flowing dry nitrogen, and then dried with molecular sieve 5A. Tetrahydrofuran 50
Add n+1 and stir vigorously. Then bromide 3-
A solution of 183 g (1.0 mol) of vinylbenze in 500 ml of dry tetrahydrofuran was gradually added dropwise over a period of 2 hours. The reaction temperature was maintained at 75° C. to 80° C., and even after the dropwise addition of the solution was completed, stirring was continued for an additional hour. The Grignard reagent thus obtained was further added to acetophenone 12 in a 3-vinylphenylmagnesium bromide solution.
A solution of 2.6 g (1.02 mol) in 500 ml of dry tetrahydrofuran was gradually added dropwise over a period of 2 hours.
反応温度は７５〜８０℃に保ち、滴下終了後もそのまま
更に１時間攪拌を続けた。しかる後、反応液を塩化アン
モニウム７５ｇの水溶液３２中に注入し、２０時間静置
した後、油層を分液して回収し、テトラヒドロフランを
留去して１−（３−ビニルフェニル）−１−フェニルエ
チルアルコールを収率８９％（アセトフェノン基準）で
得た。The reaction temperature was maintained at 75 to 80°C, and stirring was continued for an additional hour after the dropwise addition was completed. Thereafter, the reaction solution was injected into an aqueous solution 32 containing 75 g of ammonium chloride, and after standing for 20 hours, the oil layer was separated and collected, and tetrahydrofuran was distilled off to give 1-(3-vinylphenyl)-1-. Phenylethyl alcohol was obtained in a yield of 89% (based on acetophenone).
蒸留塔及び滴下漏斗付き３００ｍ１三つロフラスコに、
硫酸水素カリウム８１ｇを入れ、減圧して！５〜２０
ｍｍＨｇにし、該生成アルコールを２時間かけて滴下し
た。脱水反応して蒸留塔頂より流出した水及び油分を回
収し、分液して油層中の１−（３−ビニルフェニル）−
１−フェニルエチレンを収率１００％（原料アルコール
基準）で得た。In a 300 m 1 three-hole flask with a distillation column and a dropping funnel,
Add 81g of potassium hydrogen sulfate and reduce the pressure! 5-20
mmHg, and the produced alcohol was added dropwise over 2 hours. The water and oil that flowed out from the top of the distillation column due to the dehydration reaction are collected and separated to obtain 1-(3-vinylphenyl)- in the oil layer.
1-phenylethylene was obtained in a yield of 100% (based on raw material alcohol).
脱水反応は反応温度２００〜２５０℃で行った。The dehydration reaction was carried out at a reaction temperature of 200 to 250°C.
生成した連記化合物である１−（３−ビニルフェニル）
−１−フェニルエチレン（式Ｉ）の分析結果を以下に示
す。1-(3-vinylphenyl), which is the generated compound
The analysis results of -1-phenylethylene (Formula I) are shown below.
沸点： １３４．０〜１３５−５℃／ ２． Ｏ〜３．
０ ｍｍＨｇＩ Ｒ： （Ｎｅａｔ） ｃｍ−’
３０５０．１６９０，１４９５．
１２６０、 ９９５、９００．
８１０、 ７８０、 ７００
’Ｈ−ＮＭＲ： （にＣ１４、δｐｐｍ ）７．１
０〜７．７０ （９Ｈ，多重ｔｔＳ＞６．６５〜６
．８０ （１８５４重線）５．６５〜５．８０ （
ＩＨ，２重線）５．４５〜５．５０ （２Ｈ，，２重
線）５．２０〜５．３０ （１）１．Ｚｆｉ線）元素
分析：（ＣＩ６ＨＩ４として）
計算値 Ｃ： ９３．２０％
Ｈ： ６．８０％
実測値 Ｃ： ９３．２４％
Ｈ： ６．７６％
実施例１゜
α−（３−（１−フェニルエチニル）
フェニーレ）プロピオンアルデヒドの製造参考製造例１
で得られた１−（３−ビニルフェニル）−１−フェニル
エチレンを５０ｇ、及びロジウムヒドリドカルボニルト
リストリフェニルホスフィン０．６ｇを内容積５００！
１１の攪拌機付きオートクレーブに入れ、水素と一酸化
炭素の混ガス（モル比１：ｌ）により６０ ｋｇ／ｃｍ
２まで加圧し、反応による混合ガスの吸収が無くなるま
で反応させた。反応温度は６０℃で行った。反応終了後
、室温まで冷却して未反応混合ガスを除去してから反応
物を回収し、これを減圧蒸留にかけて濡出温度１２５．
５〜１２６．５℃／ ０．５〜１ ｍｍＨｇのα−（３
−（１−フェニルエチニル）プロピオンアルデヒドを収
率７３％で得た。ＧＣ分析の結果、α−（３−（１−フ
ェニルエチニル）フェニル）プロピオンアルデヒドとし
て９６％であった。Boiling point: 134.0-135-5°C/2. O~3.
0 mmHgI R: (Neat) cm-' 3050.1690,1495. 1260, 995, 900. 810, 780, 700'H-NMR: (C14, δppm) 7.1
0~7.70 (9H, multiple ttS>6.65~6
．． 80 (1854 double line) 5.65-5.80 (
IH, double line) 5.45 to 5.50 (2H, double line) 5.20 to 5.30 (1) 1. Zfi line) elemental analysis: (as CI6HI4) Calculated value C: 93.20% H: 6.80% Actual value C: 93.24% H: 6.76% Example 1゜α-(3-(1- Reference production example 1 for the production of phenylethynyl) phenyle) propionaldehyde
50g of 1-(3-vinylphenyl)-1-phenylethylene obtained in step 1 and 0.6g of rhodium hydridocarbonyltristriphenylphosphine with an internal volume of 500!
60 kg/cm with a mixed gas of hydrogen and carbon monoxide (molar ratio 1:l).
The pressure was increased to 2, and the reaction was allowed to occur until the mixed gas was no longer absorbed by the reaction. The reaction temperature was 60°C. After the reaction is completed, the reaction mixture is cooled to room temperature, unreacted mixed gas is removed, and the reactant is recovered, which is subjected to vacuum distillation at a wetting temperature of 125.
α-(3
-(1-phenylethynyl)propionaldehyde was obtained in a yield of 73%. As a result of GC analysis, it was found to be 96% as α-(3-(1-phenylethynyl)phenyl)propionaldehyde.
また、内部オレフィンであるエチニリデン型の二重結合
がヒドロ７オルミル化された化合物は実質的に認められ
なかった。α−（３−（１−フェニルエチニル）フェニ
ル）プロピオンアルデヒドのスペクトル分析の結果を以
下に示す。In addition, substantially no compound in which the double bond of the ethynylidene type, which is an internal olefin, was hydro7-ormylated was observed. The results of spectrum analysis of α-(3-(1-phenylethynyl)phenyl)propionaldehyde are shown below.
Ｉ Ｒ： （Ｎｅａｔ） ｃｔａ−’３０５５．２９
９５．２８５０．２７３０．１７４０．１６２０．１５
００．１４４５．１３８０．１０６０、 ９００．
７５０、’Ｈ−ＮＭＲ： （（：ＣＬ、 δｐｐｍ
）９．８０ （ＩＨ１１重線）６、９．０
〜７．４５ （９Ｈ１多重線）３．０５〜３．ｓｓ
（ＩＨ，４重線）５．０９ （２Ｈ，１重
線）１．３９〜１．４７ （３Ｈ１２重線）元素分析
： （ＣＩ７ＨｔＧｏとして）計算値 Ｃ：
８６．４４％
Ｈ： ６．７８％
０： ６．７８％
実測値 Ｃ： ａｓ、ｓｏ％
Ｈ： ６．８０％
０： ６．７０％IR: (Neat) cta-'3055.29
95.2850.2730.1740.1620.15
00.1445.1380.1060, 900.
750,'H-NMR: ((:CL, δppm
) 9.80 (IH11 double line) 6, 9.0
~7.45 (9H1 multiplet) 3.05~3. ss
(IH, quadruplet) 5.09 (2H, singlet) 1.39-1.47 (3H, doublet) Elemental analysis: (as CI7HtGo) Calculated value C:
86.44% H: 6.78% 0: 6.78% Actual value C: as, so% H: 6.80% 0: 6.70%
Claims (2)
ル）ビニルベンゼンを、遷移金属錯体カルボニル化触媒
の存在下に、水素及び一酸化炭素と反応させることによ
り下記式（II）で表されるα−（（１−アリールエテニ
ル）フェニル）プロピオンアルデヒドを製造することを
特徴とする選択的ヒドロフォルミル化方法。 ▲数式、化学式、表等があります▼式（ I ） ▲数式、化学式、表等があります▼式（II） （式中、Ｒはアリール基）(1) By reacting (1-arylethenyl)vinylbenzene represented by the following formula (I) with hydrogen and carbon monoxide in the presence of a transition metal complex carbonylation catalyst, the following formula (II) is obtained. A selective hydroformylation process characterized by producing α-((1-arylethenyl)phenyl)propionaldehyde as shown. ▲There are mathematical formulas, chemical formulas, tables, etc.▼Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼Formula (II) (In the formula, R is an aryl group)
、遷移金属錯体カルボニル化触媒の存在下に、水素及び
一酸化炭素と反応させることによりα−（３−（１−フ
ェニルエテニル）フェニル）プロピオンアルデヒドを製
造することを特徴とする特許請求の範囲第１項記載の選
択的ヒドロフォルミル化方法。(2) By reacting 3-(1-phenylethenyl)vinylbenzene with hydrogen and carbon monoxide in the presence of a transition metal complex carbonylation catalyst, α-(3-(1-phenylethenyl)phenyl) ) The selective hydroformylation method according to claim 1, characterized in that propionaldehyde is produced.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62068551A JPS63233945A (en) | 1987-03-23 | 1987-03-23 | Selective hydroformylation of diolefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62068551A JPS63233945A (en) | 1987-03-23 | 1987-03-23 | Selective hydroformylation of diolefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63233945A true JPS63233945A (en) | 1988-09-29 |
Family
ID=13377010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62068551A Pending JPS63233945A (en) | 1987-03-23 | 1987-03-23 | Selective hydroformylation of diolefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63233945A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0282066A2 (en) * | 1987-03-12 | 1988-09-14 | Nippon Petrochemicals Company, Limited | (Phenylethenyl) phenylpropionaldehyde and method for producing (benzoylphenyl) propionic acid using the same |
| US5260491A (en) * | 1990-09-24 | 1993-11-09 | New York University | Cationic rhodium bis(dioxaphosphorus heterocycle) complexes and their use in the branched product regioselective hydroformylation of olefins |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63225334A (en) * | 1987-03-12 | 1988-09-20 | Nippon Petrochem Co Ltd | Production of alpha-(3-benzoylphenyl)propionic acid |
-
1987
- 1987-03-23 JP JP62068551A patent/JPS63233945A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63225334A (en) * | 1987-03-12 | 1988-09-20 | Nippon Petrochem Co Ltd | Production of alpha-(3-benzoylphenyl)propionic acid |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0282066A2 (en) * | 1987-03-12 | 1988-09-14 | Nippon Petrochemicals Company, Limited | (Phenylethenyl) phenylpropionaldehyde and method for producing (benzoylphenyl) propionic acid using the same |
| EP0311689A1 (en) * | 1987-03-12 | 1989-04-19 | Nippon Petrochemicals Company, Limited | Process for selectively monohydroformylating diolefin |
| US4982007A (en) * | 1987-03-12 | 1991-01-01 | Nippon Petrochemicals Company, Limited | Process for selectively hydroformulating diolefin |
| US5260491A (en) * | 1990-09-24 | 1993-11-09 | New York University | Cationic rhodium bis(dioxaphosphorus heterocycle) complexes and their use in the branched product regioselective hydroformylation of olefins |
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